Liquid phase catalytic fluorination of hydrochlorocarbon and hydrochlorofluorocarbon

Abstract

A process for the catalytic fluorination of hydrochlorocarbons and hydrochlorofluorocarbons in the liquid phase. The process is useful for fluorinating hydrochloropropanes, hydrochlorofluoropropanes, hydrochloropropenes and hydrochlorofluoropropenes and most particularly useful for fluorinating 1,1,1,3,3-pentachloropropane to 1,1,1,3,3-pentafloropropane. Suitable catalysts include (i) a pentavalent molybdenum halide; (ii) a tetravalent tin halide; (iii) a tetravalent titanium halide; (iv) a mixture of a pentavalent tantalum halide with a tetravalent tin halide; (v) a mixture of a pentavalent tantalum halide with a tetravalent titanium halide; (vi) a mixture of a pentavalent niobium halide with a tetravalent tin halide; (vii) a mixture of a pentavalent niobium halide with a tetravalent titanium halide; (viii) a mixture of a pentavalent antimony halide with a tetravalent tin halide; (ix) a mixture of a pentavalent antimony halide with a tetravalent titanium halide; (x) a mixture of a pentavalent molybdenum halide with a tetravalent tin halide; (xi) a mixture of a pentavalent molybdenum halide with a tetravalent titanium halide and (xii) a mixture of a pentavalent antimony halide with a trivalent antimony halide. Products of this process are useful in a variety of applications including solvents, blowing agents, and refrigerants.

What is claimed is: 
     
       1. A fluorination process which comprises reacting CCl 3  CH 2  CHCl 2  with hydrogen fluoride and a catalyst comprising a pentavalent tantalum halide of the formula TaCl 5-n  F n , wherein n is 0 to 5, and a tetravalent tin halide of the formula SnCl 4-y  F y , wherein y is 0 to 4, in the liquid phase, wherein the molar ratio of hydrogen fluoride to CCl 3  CH 2  CHCl 2  is from 6:1 to about 15:1; the catalyst is present in an amount of from about 10% to about 20% based on the mole percent of CCl 3  CH 2  CHCl 2  and the reaction is conducted at a temperature of from about 90° C. to about 140° C. for a period of 2-8 hours to produce 1,1,1,3,3-pentafluoropropane. 
     
     
       2. The process of claim 1 which comprises reacting CCl 3  CH 2  CHCl 2  with hydrogen fluoride and an equimolar mixture of TaCl 5  and SnCl 4  as catalyst in the liquid phase, wherein the molar ratio of hydrogen fluoride to CCl 3  CH 2  CHCl 2  is from 6:1 to about 15:1 and the catalyst is present in an amount of from about 10% to about 20% based on the mole percent of CCl 3  CH 2  CHCl 2  and the reaction is conducted at a temperature of from about 90° C. to about 140° C. for a period of 2-8 hours to produce 1,1,1,3,3-pentafluoropropane. 
     
     
       3. A fluorinating process which comprises reacting at least one hydrochlorocarbon or hydrochlorofluorocarbon compound having the formula CF x  Cl 3-x  CH 2  CHF y  Cl 2-y , wherein x is 0 to 3 and y is 0 or 1 with hydrogen fluoride in the liquid phase and in the presence of a catalyst comprising a pentavalent tantalum halide of the formula TaCl 5-n  F n , wherein n is 0 to 5, and a tetravalent tin halide of the formula SnCl 4-y  F y , wherein y is 0 to 4, and wherein the product of the fluorination process comprises 1,1,1,3,3-pentafluoropropane. 
     
     
       4. The process of claim 3 wherein the hydrochlorocarbon comprises 1,1,1,3,3-pentachloropropane. 
     
     
       5. The process of claim 3 wherein the catalyst comprises TaCl 5  and SnCl 4 .